1,2,6-Trimethyltricyclo[5,3,2,02,7 ]dodeca-5-one perfume composition

ABSTRACT

1,2,6-Trimethyltricyclo[5,3,2,0 2 ,7 ]dodeca-5-one having the formula (I) ##SPC1## 
     and a process for producing this compound. This compound is useful as a perfume.

This is a Division of application Ser. No. 537,005, filed Dec. 27,1974.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a tricyclic hydrocarbon,1,2,6-trimethyltricyclo[ 5,3,2,0²,7 ]dodeca-5-one, and to a process forproducing this tricyclic hydrocarbon compound.

2. Description of the Prior Art

Amber-like fragrant substances are important starting materials for ablended perfume, and of these substances, ambergris obtainable fromsperm whales is the most expensive. The fragrance component of ambergriswas clarified by E. Laderer and L. Ruzicka in 1946 to be a substanceformed from ambrein which is a triterpene compound. Ever since, manyattempts to synthesize amber-like fragrant substances equal to thenatural material, or similar substances have been made. Some of them canbe utilized as a substitute for expensive ambergris. For example, manoolderivatives, which are diterepene compounds and can be obtained from aspecial needle-leaf tree, are widely used as such a substitute. However,in general, amber-like fragrant substances are difficult to synthesizeand moreover, special natural products are requried as a startingmaterial to synthesize amber-like fragrant substances. Therefore,synthetic amber-like fragrant substances are inevitably expensive.

SUMMARY OF THE INVENTION

This invention provides 1,2,6-trimethyltricyclo-[5,3,2,0²,7]dodeca-5-one having the formula ##SPC2##

And a process for producing 1,2,6-trimethyltricyclo[5,3,2,0²,7]-dodeca-5-one (hereinafter "Compound (I)") comprising isomerizing5,6-epoxy-1,2,6-trimethyltricyclo[5,3,2,0²,7 ]dodecane (hereinafterreferred to as "Compound (II)") with a Lewis acid.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

FIG. 1 is an infrared spectrum of Compound (I) obtained according to thepresent invention.

FIG. 2 is a mass spectrum of Compound (I) obtained according to thepresent invention.

FIG. 3 is an NMR spectrum of Compound (I) obtained according to thepresent invention.

FIG. 4 shows the stereostructural form of a ketone compound obtained byisomerization of Compound (I).

DETAILED DESCRIPTION OF THE INVENTION

Compound (I) produced according to the present invention is asesquiterpene compound having the molecular formula, C.sub. 15 H.sub. 24O, and a structure represented by the formula (I) ##SPC3##

According to this invention, Compound (I) can be obtained much morecheaply than conventional amber-like fragrant substances, and is also ofindustrial value because of its excellent amber-like fragrance.

According to the present invention, Compound (I) can be prepared byadding Compound (II) dropwise to a mixed solution of a Lewis acid suchas AlX.sub. 3, ZnX₂ and MgX₂ (wherein X is Cl, Br. or I) or a borontrifluoride-diethyl ether complex salt, etc. and a solvent inert to theLewis acid, e.g., ethers such as diethyl ether, dipropyl ether, etc.,hydrocrbons such as n-hexane, n-octane, benzene, toluene, etc.,halogenated hydro-carbons such as dicholormethane, chloroform, etc.,esters such as ethyl acetate, butyl acetate, etc., and the like, at atemperature of about -10° to 30°C, and isomerizing Compound (II) withthe Lewis acid. Alternatively the reaction can be conducted in theabsence of an inert solvent but the reaction proceeds more smoothly whenan inert solvent is employed.

When the boron trifluoride-diethyl ether complex salt is used as a Lewisacid, a suitable amount thereof is about 1/20 to 1/30 mole per mole ofCompound (II). Further, when other Lewis acids are used, a suitableamount thereof is about 0.1 to 1.2 moles per mole of Compound (II), with1 mole being preferred to achieve an isomerization which proceeds mostsmoothly and in which better results are obtained. A preferredisomerization temperture is 5° to 10°C. When the isomerizationtemperature exceeds about 30°C, a large amount of polymeric materialsare formed. The isomerization is sensitive to moisture and, thusanhydrous conditions are employed and the isomerization is preferablycarried out in a dry air or a dry nitrogen atmosphere. A sufficientisomerization time in the preferred isomerization temperture range asdescribed above is about 4 to 5 hours. After completion of theisomerization, the resulting solution is acidified, i.e., with colddilute hydrochloric acid, dilute sulfuric acid, etc., and then extractedwith a solvent such as diethyl ether, benzene, etc. Subsequently, theextract is distilled in vacuo, whereby crystalline Compound (I) can beobtained in a yield of 75% or more.

Compound (II) used as a starting material in the process of thisinvention can be produced by subjecting1,5,9-trimethylcyclododecatrine-1,5,9 (hereinafter 1,5,9-TMCDT), whichis a cyclic trimer of isoprene to an intramolecular ring closurereaction with an acid catalyst to form1,2,6-trimethyltricyclo-[5,3,2,0²,7] dodeca-5-ene (hereinafter "Compound(III)"), and treating this compound with a peracid. The intramolecularring closure reaction and the reaction with the peracid are,respectively, disclosed in copending US patent applications Ser. No.537,004, filed Dec. 27, 1974, (corresponding to Japanese PatentApplication Nos. 4207/1974 and 102646/74) and Ser. No. 537,039, filedDec. 27, 1974, (corresponding to Japanese Patent Application No.6388/1974) both filed simultaneously herewith.

Compound (I) is a fragrant substance having a rich naturalambergris-like fragrance, a peculiar wood-like odor, a camphor-likediffusibility and a so called "natural odor" reminiscent of moist earthor a sunshiney forest. When Compound (I) is absorbed on filter paper,and allowed to stand in a room at room temperture, (e.g., about20°≧30°C) the residual fragrance is very strong and lasts for over 1week. The fragrant odor of Compound (I) also is strong and even whenCompound (I) is diluted with ethyl alcohol, the average person even canperceive Compound (I) even at a one-tenthousandth dilution.

The utility value and application range of Compound (I) of thisinvention are wide as a perfumery material. That is, Compound (I) can bewidely used as a perfume, for example, as a component for a rich perfumeto a perfume for a relatively inexpensive soap, by utilizing itsresidual fragrance and economy. It is possible to use Compound (I)together with rich natural amber, or musk civet, or as a substitutetherefor by utilizing its ambergris-like fragrance, or together withnatural sandalwood oil, vetiver oil, patchouli oil, cedar oil, etc., oras a substitute therefor by utilizing its wood-like fragrance, therebyproviding a dry and rough scent necessary for a man's perfume.

Now, the present invention will be described in detail, by reference tothe following Reference Example, Examples and drawings. The examples aremerely illustrative and are not to be construed as limiting the scope ofthe present invention. Unless otherwise indicated, all parts, percents,ratios and the like are by weight.

REFERENCE EXAMPLE i. Process for Preparing1,2,6-trimethyltricyclo[5,3,2,0²,7 ]-dodeca-5-ene, Compound (III), from1,5,9-trimethylcyclododecatriene-1,5,9, 1,5,9-TMCDT:

Into a 1l three-necked flask were charged 150 g of1,5,9-trimethylcyclododecatriene-1,5,9 (melting point: 91° -92° C), 260ml of formic acid and 150 ml of dichloromethane, and the materials weremixed. The mixture was kept at a temperature of 5° to 10°C. Then, amixture of 7.5 ml of sulfuric acid and 40 ml of formic acid was addeddropwise thereto over a period of 30 minutes, while keeping thetemperature at 5° to 10°C. Subsequently, the materials were reacted withstirring at that temperature for 3 hours, and further reacted withstirring at room temperature (i.e., about 20°-30°C) for 3 additionalhours. After completion of the reaction, dichloromethane was recoveredby distillation, and formic acid was then distilled off under reducedpressure. The residue was neutralized and washed with a 3% aqueoussodium bicarbonate solution, washed with water, and dried with anhydroussodium sulfate. Then, the residue was distilled in vacuum, whereby 135 gof the frction of 1,2,6-trimethyltricyclo-[5,3,2,0²,7 ]dodeca-5-ene(75°-80°C/0.05 mmHg) was obtained.

ii. Process for Preparing Compound (II) from1,2,6-trimethyltricyclo]5,3,2,0²,7 ]dodeca-5-ene, Compound (III):

A mixture of 20.4 g (0.1 mole) of 1,2,6-trimethyltricyclo[5,3,2,0²,7]dodeca-5-ene and 17 g of sodium carbonate was added to 100 ml ofdichloromethane, and the materils were mixed and stirred while keepingthe temperature at 0° to 5°C. Then, 20.8 g (0.11 mole) of an acetic acidsolution containing 40% peracetic acid was added dropwise thereto over aperiod of 2 hours at that temperature. The materials were stirred atthat temperature for 2 hours, and further stirred at room temperaturefor 3 additional hours. Subsequently, 200 ml of water was added thereto,and the resulting solution was extracted twice with dichloromethane. Theextract was washed with an aqueous saturated sodium chloride solutionuntil the solution became neutral, and then dried with anhydrous sodiumsulfate. Dichloromethane was then recovered by distillation, and theresidue was distilled in vacuum, whereby 21 g of the fraction ofCompound (II) (85°-90°C/0.03 mmHg) was obtained.

EXAMPLE 1

13.4 g (0.1 mole) of AlCl₃ and 100 ml of n-hexane were mixed under a drynitrogen atmosphere, and the mixture was kept at 0° to 10°C. 22 g (0.1mole) of Compound (II) was added dropwise thereto over a period of 1hour. The materials were stirred at that temperature for 1 hour, andfurther stirred at room temperature for 2 additional hours. Then, thereaction solution was poured into 100 ml of cold dilute hydrochloricacid (6N), and the solution was extracted with n-hexane. The extract wasdried with anhydrous sodium sulfate, and n-hexane was then distilledoff. Subsequently, the residue was distilled in vacuum, whereby 20 g ofthe fraction (105°-110°C/0.05 mmHg) corresonding to Compound (I) wasobtained. By recrystallizing this compound from methanol, 17.6 g ofprism-like crystalline Compound (I) having a melting point of 99.5° to100.5°C was obtained in a yield of 80%.

    ______________________________________                                        Elemental Analysis:                                                                             C         H                                                 Calculated (%):   81.76     10.98                                             Found (%):        81.75     10.98                                             IR Spectrum:    1710 cm.sup..sup.-1 (ν C=0)                                MAS Spectrum:   M.sup.+ 220 (molecular ion)                                                   M.sup.+--CH.sub.3 205                                                         M.sup.+--CO 192                                               NMR Spectrum:                                                                  ##STR1##           (a)0.95ppm(3H,s) (b)1.20ppm(3H,s) (c)0.89ppm(3H,d,J=7c                       ps) (d)2.77ppm(1H,q,J=7cps) (e)2.37ppm(2H,m)               X-ray Crystal Structural Analysis (direct method):                            Lattice constant:                                                                          a=7.975A,  b=13.225A, c=7.147A                                                α=95.7°,                                                                    β=60.0°,                                                                     γ=104.2°                      Space group: P1,                                                                           Z=2                                                              Values (A) of X, Y and Z as solid coordinates:                                Atom       RX         RY         RZ                                           ______________________________________                                        C1         0.9791     5.7703     1.7584                                       C2         2.3424     5.6967     2.4672                                       C3         3.1955     4.4961     2.0121                                       C4         2.3586     3.2151     1.9691                                       C5         3.0098     1.9672     1.2955                                       C6         3.6074     2.3334     -0.0927                                      C7         2.4712     2.8519     -1.0345                                      C8         1.5720     3.8637     -0.3559                                      C9         1.1293     3.4170     1.0436                                        C10       0.2013     4.4893     1.6283                                        C11       0.5477     1.9829     0.9738                                        C12       1.7833     1.0214     1.1082                                        C13       -1.1340    4.7008     0.8295                                        C14       1.9438     2.8689     3.4240                                        C15       4.1078     1.2928     2.1657                                       01         0.5492     6.8548     1.4110                                       ______________________________________                                    

Bonding angle among atoms from the solid coordinates:

    ______________________________________                                        Three Atoms     Bonding Angle                                                 ______________________________________                                                        (degree)                                                      C2-C1-C10       117.21                                                        C1-C2-C3        113.06                                                        C3-C4-C9        109.94                                                        C5-C4-C14       109.74                                                        C4-C5-C12       102.04                                                        C6-C5-C15       109.29                                                        C6-C7-C8        112.52                                                        C4-C9-C10       110.05                                                        C8-C9-C11       109.68                                                        C1-C10-C13      111.65                                                        C5-C12-C11      104.92                                                        C2-C1-O1        119.15                                                        C2-C3-C4        110.94                                                        C3-C4-C14       107.85                                                        C9-C4-C14       112.11                                                        C4-C5-C15       113.57                                                        C12-C5-C15      111.06                                                        C7-C8-C9        112.68                                                        C4-C9-C11       101.76                                                        C10-C9-C11      115.93                                                        C9-C10-C13      114.50                                                        C10-C1-O1       123.46                                                        C3-C4-C5        116.95                                                        C5-C4-C9        100.20                                                        C4-C5-C6        110.94                                                        C6-C5-C12       109.74                                                        C5-C6-C7        109.65                                                        C4-C9-C8        110.69                                                        C8-C9-C10       108.58                                                        C1-C10-C9       108.39                                                        C9-C11-C12      105.50                                                        ______________________________________                                    

The stereostructural formula shown in FIG. 4 can be derived from theforegoing values.

Molecular Formula: C₁₅ H₂₄ O

From the foregoing results, Compound (I) was determined to have thefollowing stereostructural formula (III) ##SPC4##

EXAMPLE 2

The reaction was carried out under the same conditions as described inExample 1, except that 0.57 g (0.004 moles) of boron trifluoride-diethylether complex salt was used in place of 13.4 g (0.1 mole) of AlCl₃,whereby 17.2 g of Compound (I) was obtained in a yield of 78%.

EXAMPLE 3

The following formulation is suitable as a base for a perfume or aneau-de-cologne.

    ______________________________________                                                           g                                                          ______________________________________                                        Civet Absolute      10                                                        Musk Absolute        5                                                        Oak Moth Absolute   30                                                        Vanilla Absolute    10                                                        Musk Ambrette       80                                                        Sandalwood Oil      50                                                        Patchouli Oil       80                                                        Methyl Ionone       30                                                        Vetiver Oil         100                                                       Eugenol             20                                                        Phenylethyl Alcohol 30                                                        Geraniol            30                                                        Benzyl Acetate      30                                                        Jasmine Absolute    20                                                        Hexylcinnamic Aldehyde                                                                            50                                                        Linalool            50                                                        Linalyl Acetate     50                                                        Bergamot Oil        125                                                       Compound (I)        50                                                                            850g                                                      ______________________________________                                    

EXAMPLE 4

The following formulation is suitable for a soap perfumery.

    ______________________________________                                                          g                                                           ______________________________________                                        Ethylene Brassylate                                                                              90                                                         Sandalwood Oil     50                                                         Oakmoth Resinoid   10                                                         Patchouli Oil      50                                                         Coumarin           30                                                         Bornyl Acetate     15                                                         Citronellol        60                                                         Tetrahydrogeraniol  5                                                         Petigrain Oil      30                                                         Lavandine Oil      80                                                         Stearyl Acetate    15                                                         Pineneedle Oil     10                                                         Linalool           185                                                        Linalyl Acetate    120                                                        Compound (I)       50                                                                            800g                                                       ______________________________________                                    

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A perfume composition containing1,2,6-trimethyltricyclo[5,3,2,0²,7 ] dodeca-5-one having the formula (I)##SPC5##and other perfume ingredients.